Pigmented rubber hydrohalides



Patented Oct. 10, 1939 tion of Delaware PIGMENTED RUBBER HYDROHALIDES James B. Holden, Akron, Ohio, assignor to Wingfoot Corporation, Wilmington, Del., a corpora- No Drawing. Original application February 8,

1936, Serial No. 62,992. Divided and this application August 30, 1938, Serial No. 227,547

4 Claims.

This invention relates to the hydrohalide derivatives of rubber. More particularly, it relates to the compounding of such materials with pigments to yield very desirable products.

Hydrohalide derivatives of rubber are Well known. It is also known that this type of material can be utilized to form films of excellent moistureproofness and other desirable physical characteristics. Rubber hydrochloride may be taken as representative.

One of the outstanding difficulties with films made of rubber hydrochloride is their tendency to deteriorate through ageing. Various methods have been proposed for retarding this deterioration.

It has now been discovered that this deterioration may be greatly retarded by incorporating into the rubber hydrochloride certain pigments. Besides imparting longer life to the film, certain of these pigments produce other outstanding effects of great usefulness and value.

The pigments are preferably added to the rubber hydrochloride cement prior to the spreading and formation of the film.

Any of the known methods of securing proper dispersion may be employed. It has been found, for example, that dry aluminum powder may be added directly to a seven percent solution. of rubber hydrochloride in benzene and a satisfactory 30 dispersion obtained by simple mixing, as by rolling or the use of a high speed stirrer. This does, however, tend to entrap air in the cement and produce pinholes in the subsequently formed film. This pinhole formation can be laregly eliminated by allowing the cement to stand before spreading so that the air can separate. Perhaps even better results are obtained by using the aluminum in the paste form in which it is obtainable wetted with a gasoline fraction.

Of course, the finer particle pigments disperse with more difiiculty and it may become advisable to grind the pigment, in a ball mill or other wise, with the rubber hydrochloride cement or with the plasticizer which is to be incorporated in the cement.

One method which has been found very satisfactory with fine particle pigments, such as carbon black, has been to mill the pigment into a resin such as the chlorostannic acid reaction 50 product of rubber. This pigmented resin is then dissolved in a small amount of benzene, with excellent pigment dispersion and this dispersion is added to the rubber hydrochloride cement.

Any other method of adding the pigment may be employed if desired.

Following are the formulae of a number of representative pigmented rubber hydrochloride films which demonstrate the invention, Sample A being an unpigmented control. Proportions are parts by weight. The term Pliolite is used to designate the chlorostannic acid reaction product of rubber.

Formula 100.00 parts rubber hydrochloride. 10.00 parts butyl stearate. 0.75 part hexamethylcne tetrarniue.

100.00 parts rubber hydrochloride. 10.00 parts butyl stcaratc.

8.20 parts Pliolite.

13.90 parts titanium oxide.

0.75 part hexamethylcne tetramine.

100.00 parts rubber hydrochloride. 10.00 parts butyl stearate.

16.50 parts Pliolitc 5.00 parts para red toner.

0. part hexamethylene tetra-mine.

100.00 parts rubber hydrochloride. 10.00 parts butyl stearate.

16.00 parts Pliolite.

4.60 parts chrome green.

3.30 parts lead chromate.

075 part hexamethyleue tetramine.

100.00 parts rubber hydrochloride. 10.00 parts butyl stearate.

24.00 parts Pliolitc.

17.20 parts Prussian blue.

12.80 parts titanium dioxide. 0.75 part hcxamethylene tetramine.

100.00 parts rubber hydrochloride. 1000 parts butyl stearate.

9.60 parts Pliolite.

4.10 parts red iron oxide.

2.00 parts carbon black.

0.75 part hexamethylene tetramine.

100.00 parts rubber hydrochloride.

. arts butyl stearate.

6.50 parts Pliolitc.

.00 parts carbon black. I .75 part hcxamethylenc tetramme.

0.00 parts rubber hydrochloride. 10.00 parts butyl stearate.

2.80 parts aluminum powder. 0.75 part hexamcthylene tetramme.

Films of these compositions and 0.001 inch thick were made and exposed to sunlight behind window glass on a roof at an angle of 45 .degrees facing south. The following table shows the times required for the various films to become These data show the marked differences in effect of different pigments.

Simple A, a clear,

unpigmented film, is the control. Film B is much inferior to the control, C and D are somewhat in- 60 ferior, E is about the same, and F, G and H are very much superior. Thus, various pigments affect the ageing qualities of the fil not only in degree but actually in kind, i. to advantage or disadvantage. It is shown that some pi very greatly increase the resistance o ageing or" the film.

Of course, this method of adding to ful life of the film cannot be e'nployec. when a clear, transparent product is ed. Bewever, many applications arise in which opacity and color are no detriment or even an d? According to the data above given, carbon black, red iron oxide, and afiuminur are out standing in anti-ageing action. Prussian blue also seems to have some benefi ial effect. Sample the Prussian blue ver' successfully neutralizes the detrimental effect of titanium dioxide which is demonstrated by Sample B.

Thus, it is intended that the in ention shall include the use of pigments to improve the ageing of the film over that of the uncompounded material or to neutralize the ill effects of other compounding ingredients.

Also, it is not intended that the vention shal be limited to the use of only 13110353 materials which are shown by the included data to be beneficial. There are many other pigments and com-- poundings which are operable and the invention includes all of these.

It is not known for certain what mechanism is involved in the protective action of these pigmerits. It appears that they may function in two ways. It is known that ultra-violet l t causes rubber hydrochloride to deteriorate. it -s also known that aluminum reflects ultra-violet light very efiiciently. It is also, of course, well known. that black. and other dark bodies are efficient absorbents of energy. It thus seems logical to suppose that these pig: nts function either by reflecting the ultra-violet ener y absorbing it and converting it to a less det tal form such as the longer wave-lengt. energy. Any pigment operating in either of these manners would be operable.

The product obtained by incorporating finely divided aluminum into rubber l'iydrocl'iloride posscsses other very desirable and noteworthy charactcristics in addition to its improved ageing qualities. In the first place, it possesses a very good metallic luster, which suggests its use. on an appearance basis, as an alternative for me talllc aluminum foil. In several respects, it is very much superior to metallic aluminum foil. The resistance to the diffusion of Water vapor, carbon dioxide, and other gases is higher for rubber hydrochloride containing powdered aluminum than for the unpigmented film. This value is much superior to that obtained with metallic aluminum foil, This last perhaps surprising fact is explained by the fact that aluminum, in being rolled down to thin foil, tends to develop minute pinholes which render it less impervious to gas diffusion than might be supposed. My new prodnot is also much stronger than aluminum foil, particularly in its resistance to tearing and creasing. Also, it retains the characteristics of unpigmented rubber hydrochloride of being heat scalable at moderate temperature, as, for example, at 230 F.

A wide variety of appearance effects are obtainable in this film of metallic appearance, as by the addition of dyes, the blending with other pigments, and the use of colored aluminum pigments.

Rubber hydrochloride film containing finely divided aluminium therefore, one of the preferred forms of the invention. However, many other compoundings are also included, as heretofore explained.

Thus, although only the preferred forms of the invention have been described in detail, it will obvious to those skilled in the art that many cations may be made therein without deg from the spirit of the invention or the sco e of the appended claims, in which it is intended to cover by suitable expression all features of patentable novelty inherent in the invention.

This application is a division of my prior application Serial No, 62,992, filed February 8, 1936.

What I claim is:

1. A rubber hydrohalide of increased resistance to ageing containing Prussian blue.

A rubber hydrohalide film of increased resistance to ageing containing Prussian blue.

3. A rubber hydrochloride film containing Prussian blue.

i. A flexible, tear-resistant, heat-scalable film having high resistance to the diifusion of water vapor and having high resistance to ageing, which film comprises rubber hydrochloride and Prussian blue.

JAB/IE8 B. HOLDEN. 

